Light-sensitive silver halide photographic material containing as a stabilizer a hydroimidazo-s-triazine

ABSTRACT

A light-sensitive silver halide photographic material containing in at least one of its photographic layers a hydroimidazo-striazine compound as a stabilizer.

United States Patent Sato et al.

[ 1 May 16, 1972 [54] LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPHIC MATERIAL CONTAINING AS A STABILIZER A HYDROIMIDAZO-S-TRIAZINE [72] lnventors: Shui Sato; Tomio Nakajima; Masayuki Shono, all of Tokyo; Teruo Kagami, lrimishi, all of Japan [73] Assignee: Konishiroku Photo Industry Co., Ltd.,

Tokyo, Japan [22] Filed: Dec.4, 1969 [21] Appl.No.: 882,311

[30] Foreign Application Priority Data Dec. 4, 1968 Japan ..43/88338 [52] U.S. Cl ..96/l09, 260/239] Primary Examiner-Norman G. Torchin Assistant ExaminerRichard E. Fichter Attorney-Waters, Roditi, Schwartz & Nissen [57] ABSTRACT A light-sensitive silver halide photographic material containing in at least one of its photographic layers a hydroimidazo-striazine compound as a stabilizer.

3 Claims, No Drawings LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPIIIC MATERIAL CONTAINING AS A STABILIZER A HYDROIMIDAZO-S-TRIAZINE This invention relates to a light-sensitive silver halide photographic material containing in at least one of its photographic layers a hydroimidazo-s-triazine compound as stabilizer, and the object of the invention is to provide a light-sensitive silver halide photographic material which is stable in photographic properties under high temperature and high humidity conditions and is storable for a long period of time.

It has been known that when stored for a long period of time particularly under high temperature and high humidity conditions a light-sensitive photographic material prepared by using a silver halide photographic emulsion generally suffers from such drawbacks that it is decreased or increased in photographic speed and forms the so-called emulsion fog which, after the photographic material has been exposed, brings about the blackening of unexposed portion. The formation of such fog during storage of photographic material and change with time in photographic speed characteristics of photographic emulsion after preparation are not desirable. With an aim to prevent photographic materials from deterioration in photographic properties due to lapse of time or to change of external conditions, stabilizers have heretofore been incorporated into the photographic layers of light-sensitive photographic materials, e.g. emulsion layer, interlayer, sub layer or protective layer. Preferable as such stabilizers, tetrazaindenes have been known heretofore. However, the conventional stabilizers are not always satisfactory and tend to cause deterioration of fog, sensitivity and the like photographic properties, during storage under high temperature and high humidity conditions. These drawbacks are obviously undesirable for lightsensitive materials to be used in Japan where high temperature and high humidity are brought about in summer.

In view of such circumstances, we made various studies to find that when a hydroimidazo-s-triazine compound exists in at least one photographic layer of a light-sensitive silver halide photographic material, such as emulsion layer, sublayer, interlayer or protective layer, the light-sensitive photographic material is markedly stable to deterioration in photographic characteristics during storage for a long period of time, particularly during storage under high temperature and high humidity conditions.

Hydroimidazo-s-triazine compounds can be synthesized by isomerization of aziridene rings with sodium iodide and triethylamine hydrochloride or rhodanate disclosed in Journal of the American Chemical Society, Vol. 83, page 2570, and Journal of Organic Chemistry, Vol. 25, page 46l, or by dehydrochlorination reaction of B-chloroethylamino groups disclosed in Journal of the American Chemical Society, Vol. 77, page 5922. Among such hydroimidazo-s-triazine compounds, those which are particularly useful in the present invention are represented by the following general Formulas I, ll, Ill and lV:

Q LR,

General Formula (II) General Formula (I\') ELL,

(wherein Rs, which may be same or different groups, represent individually H, --CH;, or -C H R and R,, which may be same or difierent groups, represent individually -OH, OCH;,, SCI-l or NH,; R represents H, -NH,, OCH;, or -OC H X represents -NH(CH ),,NH,

; and n is an integer of 2 to 6) Typical examples of the above-mentioned hydroimidazo-striazine compounds employed in the present invention include the following compounds:

(l) l-hytlroxy-2-meLh0xy-(i,7-(lihydroimiduzo (1,2-11) s-trinzine (2) 2,4-(1ihydroxy fiflalihydroimidazo (1,2-a) s-triazine OII (3) 'J l-(limninu-(iJ-dihydroimirlnzu (1,211) s-trizizim- Nil:

N N NJ-NlI I I (4) 5m0tl1oxy-2,3,8,9-tetml1ydrodlmndazo (1,2-n:1,2"c) s-trlazlue 3 N N f l i OCH (5) g-amiit0-2,3,8,9-tetrahydrodiimidazo (1,2-a:l,2-c) striazine hydroilori e l /L l N Nin-irm (6) 2,8 (r 3,0)-(limethyl-5-eth0xy2,3,8,9-tctrahydrodiimidazo (12a:

N O C211 hexamcthylcnediamine p-phcnylenediaminc AJQLN 12) N,N-bis [2.8 (or 3,9)-diethyl-2,3,8,9-tetrahydrodiimidazo (1,2-a: 1,2-c) s-triazine-5-yl] trimethylenediamino (13) 2,3,6,7,10,ll-Hexahydrotriimidazo (1,2-a:1,2-c:1, 2"-e) s-triazine (1 4) 2,6,}? (or 3,7,11)-trimethyl-2,3,6,7,10,ll-hexahydrotriimidazo (1,2-a: 1',2 -c:1,2 -e) s-triazinc Concrete synthesis examples of the above-mentioned compounds are shown below.

SYNTHESIS EXAMPLE 1 Synthesis of the Compound 1 A mixture comprising 5.3 g. of 2-fl-chloroethylamino-4,6- dimethoxy-s-triazine, 8.0 cc. of 3.0 N-caustic soda and 22 cc. of ethyl alcohol was boiled for 2 hours, and then the solvent was removed by distillation under reduced pressure. The residual viscous solid was recrystallized two times from water to obtain 1.4 g. of the above-mentioned compound, mp 212 Elementary analysis for c,H,N,o,=

Calculated (9%) C: 42.86 H: 4.80

N:33. 2 Found (70) C: 42.51 H:5.l0 N32. 1

Synthesis of the Compound 5 A mixture comprising 2.7 g. of 2,4-di(,B-chloroethylamino-6 -chloro-s-triazine, 10 cc. of 28 percent aqueous ammonia solution was reacted for 3 hours in a bath at C., whereby the mixture once became a transparent solution but soon formed a white precipitate. After cooling the liquid, the precipitate was recovered by filtration and was extracted with hot water. Thereafter, the extract was combined with the filtrate, and the mixed liquid was concentrated under reduced pressure and was cooled to deposit a crystalline mass. The mass was recovered by filtration and was recrystallized from water to obtain 0.5 g. of the above-mentioned compound, m.p. 250 C.

Elementary analysis for C H ClN,,:

Calculated (70) C: 39.20 H: 5.13 N: 39.2 Found (70) C: 38.87 H: 5.l7 N: 39.!7

Cl: 16.60 Cl: 16.64

SYNTHESIS EXAMPLE 3 Elementary analysis for C H N ,2H O:

Calculated (7:) C: 50.61 H: 7.22 Found (7%) C: 50.24 H: 7.21

SYNTHESIS EXAMPLE 4 Synthesis of the Compound 13 A solution of 3.0 g. of triethylene melamine and 1.5 g. of sodium iodide in cc. of acetone was allowed to stand at room .temperature for 24 hours to deposit a needle-like crystalline mass. The mass was recovered by filtration, was washed with acetone and was then recrystallized from water to obtain 2.3 g. of the above-mentioned compound, m.p. above 250 C.

Elementary analysis for C,H,,N,%l-l,0:

Calculated (70) C: 50.70 H: 6.15 N: 39.41 Found C: 51.15 H: 6.24 N: 39.82

SYNTHESIS EXAMPLE 5 graphic stabilizers not only for monochromatic photographic materials but also for color photographic materials.

The amount of the hydroimidazo-s-triazine compound to be added to or incorporated into the photographic layers of a 5 light-sensitive photographic material varies depending not Y" of the q f p l 14 only on the kind of the compound but also on the kind of the A p 'l p py 'f f y f f emulsion employed, i.e. whether the emulsion is silver from cyanunc Chloride f P py sofhum f chloride, silver bromide or silver iodide, the content of the and acetone was l the same manner as synfhesls solid solution, the particle size and photographic sensitivity of Example 013mm the above-mentioned compound In the the silver halide emulsion, and the desired degree of stabilizaform of whlte sohdtion. Generally, however, the compound is added in an amount of about 0.0 1-8 g. per mole of silver halide. Elementary analysis for C H N The followin exam les illustrate the resent invention but Calculated C: 58.52 H: 7.37 N: 34.12 th v d th b dT Fmmdm) Q5809 3M2 N: 3433 15 em en ion 5 no lml e ere yan various mo llca ions are possible within the scope of the invention.

Other hydrolmidazo-s-trlazlnecompounds than those men- EXAMPLE 1 tloned above can also be synthesized according the the abovementioned synthesis examples. A neutral negative silver iodobromide emulsion containing The thus obtained hydroimidazo-s-triazine compounds 5 mole percent of silver iodide was charged with a gold senshould be present in the photographic layers of light-sensitive sitizer and was subjected to second ripening, and the thus photographic materials according to any procedures for incortreated emulsion was divided into six portions. One portion of porating conventional photographic stabilizers into the layers the emulsion was coated, as it was, onto a support to prepare a of the constituents. For example, the present compound may control sample. Another portion was charged with an aqueous be added to a photographic emulsion in the form of a solution 2 solution of mg. per 0.035 mole of said silver halide of the in a suitable inorganic or organic solvent such as a mixed soluknown stabilizer 4-hydroxy 6methyll ,3,3a,7-tetrazaindene, tion of water and a lower alcohol, a lower alcohol, dimethyl and was coated onto a support to prepare a comparative samsulfoxide or the like. The present compound may be added at ple. The other four portions were individually charged with any time during the step for preparation of photographic methanol solutions of the compounds set forth in Table l in emulsion, and may be previously incorporated into the start- 30 such amounts as shown in the table, and were coated onto suping materials for preparation of the emulsion. Generally, howports to prepare samples of the present invention. These samever, it is preferable and is most effective to add the comples were subjected to ordinary sensitometry according to the pound after completion of the second aging. JlS method K-7604 to obtain the results as set forth in Table The emulsion to be used for preparation of the present l. The photographic speed was shown in terms of a relative photographic material may have been subjected to noble value calculated by assuming as 100 the speed of the control metal sensitization, sulfur sensitization, sensitization with alsample immediately after coating.

TABLE 1 After incubation After incubation at Immediately at 55 C. for 3 C. and humidity after coating days of 80% for 3 days Amount added Relative Relative Relative Sample Stabilizer (mg.) Fog speed Fog speed Fog speed (olltl'ol sample 0.13 100 0.62 81 0.34 110 Comparative Sample Above-mentioned tcti'azalndeile 30 0 13 100 0.12 94 0.08 80 EOIllpOllllg g 100 0.10 08 0.10 101 x ompouli J7 0. 2 100 0. 12 98 SW91" P1050 Colnpoulld l0)... 35 0 10 103 0.12 102 0.11 101 Compound (13) 30 0 11 100 0.12 97 0 12 9!) kylene oxide polymer or the like chemical sensitization, optical sensitization or super color sensitization. The hydroimidazo-s-triazine compounds of the present invention do not injure the photographic speed attained by said sensitization and inhibit the increase of fog generated thereby, with the result that the resulting photographic materials can be more effectively enhanced in light-sensitivity increase due to said sensitization, and can be prevented from lowering in photographic speed and increase in fog during storage, particularly under high temperature and high humidity conditions.

In preparing the light-sensitive silver halide photographic materials of the present invention, the above-mentioned compounds in accordance with the present invention may be used, without any detrimental interactions, in combination with other photographic additives, e.g. other stabilizers, coating aids, hardeners, toners, matting agents and the like.

Further, in the case of color photographic materials containing in the emulsion layers thereof large amounts of color formers or containing dispersions of color formers dispersed as protective colloids by use of high boiling oil or low boiling oil or the mixture of both, the compounds of the present invention can inhibit the generation of color fog due to fog of silver halide emulsions, and hence, are effective as photo- As is clear from Table 1, it is understood that the light-sensitive silver halide photographic materials of the present invention show markedly excellent stability in fog and speed, and have such properties that they are less in desensitization under high temperature and high humidity conditions than the known stabilizer.

EXAMPLE 2 The same photographic emulsion as in Example 1 was subjected to second ripening and was the incorporated according to an ordinary procedure with the color former, l-(4-phenoxy-3'-sulfophenyl)-3-heptadecyl-5 pyrazolone, to prepare a color photographic emulsion. This emulsion was divided into three portions. One portion of the emulsion was coated, as it was, onto a support to prepare a control sample. The other two portions were individually charged with methanol solutions of 30 mg. and 40 mg. per 0.035 mole of said silver halide of the present Compound 8, and were coated onto supports to prepare samples of the present invention. These samples were exposed by means of a sensitometer, were developed with a color developing solution composed mainly of diethyl-p-phenylenediamine, and were subjected to ordinary bleaching, fixing and water-washing treatments. The results were as shown in Table 2.

In. "5 nero TABLE 2 After incubation at 50 C. and Immediately After incubation humidity of 80% after coating at 55 C. for 3 days [01-3 days Amount added Relative Relative Relative Sample Stabilizer (mg.) Fog speed Fog speed Fog speed Control sample .t 12 100 26 35 19 96 Sample of the present invention i? g As is clear from the above table, the light-sensitive photo- N R graphic materials according to the present invention were 1'1 markedly excellent in fog and photographic speed particularly N N -1t under high temperature and humidity conditions, and could R give excellent color images without any color fog. l

What we claim is: N N l. A light-sensitive silver halide photographic element com- N prising at least one photographic layer containing 0.0l-8g./ J mole of silver halide of a hydroimidazo-s-triazine compound, R- -R (IV) 20 having one of the following general Formulas I, II, III and IV wherein Rs, which may be same or different groups, represent individually H, CH;, or C H R and R which may be same or different groups, represent individually OH, OCH SCH or NH R represents H, NH OCH or OC H X represents NH(CH ),,NH,

2. A light-sensitive silver halide element as claimed in claim 1, wherein said element is a light-sensitive silver halide color photographic element.

3. A light-sensitive silver halide photographic element as claimed in claim 2, wherein said photographic layer is an emulsion layer, interlayer, sublayer or protective layer.

lOl036 0519 

2. A light-sensitive silver halide element as claimed in claim 1, wherein said element is a light-sensitive silver halide color photographic element.
 3. A light-sensitive silver halide photographic element as claimed in claim 2, wherein said photographic layer is an emulsion layer, interlayer, sublayer or protective layer. 